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WO2009113392A1 - Electromagnetic steel sheet having insulating coating film with excellent thermal conductivity therein, and process for production thereof - Google Patents

Electromagnetic steel sheet having insulating coating film with excellent thermal conductivity therein, and process for production thereof Download PDF

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Publication number
WO2009113392A1
WO2009113392A1 PCT/JP2009/053383 JP2009053383W WO2009113392A1 WO 2009113392 A1 WO2009113392 A1 WO 2009113392A1 JP 2009053383 W JP2009053383 W JP 2009053383W WO 2009113392 A1 WO2009113392 A1 WO 2009113392A1
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WO
WIPO (PCT)
Prior art keywords
steel sheet
chromic acid
insulating coating
terms
electrical steel
Prior art date
Application number
PCT/JP2009/053383
Other languages
French (fr)
Japanese (ja)
Inventor
和年 竹田
健司 小菅
真治 永川
修 稲岡
Original Assignee
新日本製鐵株式会社
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Application filed by 新日本製鐵株式会社 filed Critical 新日本製鐵株式会社
Priority to JP2010502761A priority Critical patent/JP4608600B2/en
Priority to KR1020107017962A priority patent/KR101168509B1/en
Priority to CN200980105538.6A priority patent/CN101946024B/en
Publication of WO2009113392A1 publication Critical patent/WO2009113392A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
    • C23C22/26—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also organic compounds
    • C23C22/28—Macromolecular compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/16—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets
    • H01F1/18—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets with insulating coating

Definitions

  • the present invention relates to an electromagnetic steel sheet having an insulating coating excellent in thermal conductivity suitable for an iron core or the like of electrical equipment and a method for manufacturing the same.
  • Patent Document 1 As a technique related to the insulating coating of an electrical steel sheet, as disclosed in Patent Document 1, a treatment liquid mainly composed of an organic resin emulsion such as dichromate and vinyl acetate, a butadiene-styrene copolymer, an acrylic resin, etc. There is a method of forming an insulating film by using. Moreover, as disclosed in Patent Document 2, a chromic acid aqueous solution, an emulsion type resin, and an organic reducing agent are mixed, and a readily soluble aluminum compound, a divalent metal oxide, etc., H 3 BO 3 , and chromic acid are mixed.
  • Patent Document 2 a chromic acid aqueous solution, an emulsion type resin, and an organic reducing agent are mixed, and a readily soluble aluminum compound, a divalent metal oxide, etc., H 3 BO 3 , and chromic acid are mixed.
  • the molar ratio of Me 2+ / Al 3+ in the solution is 0 to 7.0
  • the molar ratio of (Al 3+ + Me 2+ ) / CrO 3 is 0.2 to 0.5
  • the molar ratio of H 3 BO 3 / CrO 3 There is a method of forming an insulating film using a treatment liquid having a thickness of 0.1 to 1.5.
  • Patent Document 3 after application and baking of a treatment liquid containing chromic acid, a readily soluble divalent and / or trivalent basic metal compound, an aqueous emulsion resin, boric acid, and an organic reducing agent, and after strain relief annealing, A magnetic steel sheet is described in which chromium is hexavalent chromium and is present on the outermost surface layer of the coating as measured by X-ray photoelectron spectroscopy.
  • the thermal conductivity of oxide-based insulating coatings is much lower than that of metals. For this reason, heat is not easily transmitted in the stacking direction of the iron cores, and heat dissipation in this direction does not contribute much to the heat dissipation of the entire motor.
  • An electrical steel sheet having an insulating coating excellent in thermal conductivity includes an electrical steel sheet and an insulating coating formed on a surface of the electromagnetic steel sheet, and the insulating coating includes a metal chromate salt, Styrene resin, acrylic resin, epoxy resin having a crystallization ratio of 0.01 to 0.5 parts by weight with respect to 1 part by weight of the chromic acid metal salt (in terms of CrO 3 ) 100% of a chromic acid compound obtained by converting a chromium hydroxide compound as a chromic acid compound into chromium trioxide (Cr 2 O 3 ) as a main component, one or a mixture of two or more kinds of polyimide resins or a copolymer. In contrast, it is characterized by containing 30% or more in terms of chromium trioxide (Cr 2 O 3 ).
  • a method of manufacturing an electrical steel sheet having an insulating coating having excellent thermal conductivity a step of applying a predetermined coating liquid to the surface of the electrical steel sheet, and forming the insulating coating by drying the predetermined coating liquid And converting the resin solid content to 0.1 parts by weight with respect to 1 part by weight of the chromic acid metal salt and the chromic acid metal salt (in terms of CrO 3 ) as the predetermined coating liquid.
  • a styrene resin emulsion 01 to 0.5 parts by weight of a styrene resin emulsion, an acrylic resin emulsion, an epoxy resin emulsion, a polyimide resin dispersion, or a mixture or copolymer of styrene resin emulsion, acrylic resin emulsion, epoxy resin dispersion having a crystallization rate of 10% to 50% And a main component, and a step of forming the insulating coating using a polyol compound as a chromic acid reducing agent added in an amount of 1.2 to 3.6 times the chromic acid equivalent, And heating the predetermined coating liquid at a rate of 10 ° C./second to 35 ° C./second in a temperature range of 50 ° C. to 200 ° C.
  • the electrical steel sheet according to the embodiment of the present invention preferably contains Si: 0.1% by mass or more and Al: 0.05% by mass or more.
  • Si As the Si content increases, the electrical resistance increases and the magnetic properties improve, but the brittleness increases. For this reason, it is preferable that content of Si is less than 4.0 mass%.
  • Al As the Al content increases, the magnetic properties are improved, but the rollability is lowered. For this reason, it is preferable that content of Al is less than 3.0 mass%.
  • Mn etc. may be contained in addition to Si and Al.
  • the Mn content is preferably 0.01% by mass to 1.0% by mass.
  • the content of transition elements such as Cr and Ni is preferably less than 0.1% by mass, and more preferably less than 0.01% by mass.
  • the content of typical elements such as S, N and C is preferably less than 100 ppm, and more preferably less than 20 ppm.
  • the slab having the above components is hot-rolled, wound into a coil shape, annealed as necessary, and has a thickness of 0.15 mm to 0.005. Cold-roll to about 5 mm and further anneal.
  • the surface roughness of the electrical steel sheet according to the embodiment of the present invention is preferably relatively small. This is to obtain high adhesion.
  • the center line average roughness Ra in the rolling direction and the direction orthogonal to the rolling direction is preferably 0.8 ⁇ m or less, and more preferably 0.5 ⁇ m to 0.1 ⁇ m. This is because if the average roughness Ra is larger than 0.8 ⁇ m, sufficient bending adhesion may not be obtained.
  • the chromic acid metal salt becomes a solid content when an aqueous solution mainly containing dichromic acid and metal ions is dried.
  • the metal species is preferably contained in a molar ratio of 0.5 to 1.3 with respect to dichromic acid regarded as a divalent anion. Further, when the metal species is divalent, the molar ratio of the metal species is more preferably 1.05 to 1.15. When the metal species is trivalent, the molar ratio of the metal species is 0.00. It is more preferably 7 to 0.77.
  • the metal ions are preferably light metal ions such as Li, Al, Mg, Ca, Sr, and Ti, and particularly preferably alkaline earth metal ions such as Mg.
  • metal ions When metal ions are dissolved in the dichromic acid solution, metal ion oxides, carbonates, or hydroxides may be used.
  • an alkali metal ion such as Li and an alkaline earth metal ion such as Mg are dissolved, an attempt to dissolve the metal itself reacts violently, so it is preferable to use an oxide or hydroxide. .
  • the chromium of the applied dichromic acid is reduced from hexavalent to trivalent, The portion is chromium trioxide (Cr 2 O 3 ), and 10% to 20% of chromium is chromium hydroxide (Cr (OH) 3 ).
  • the ratio of chromium hydroxide (Cr (OH) 3 ) may increase more than the conventional one depending on conditions. I found out. That is, the present inventors have found that the amount of chromium hydroxide (Cr (OH) 3 ) produced depends on the amount of polyol compound added and the rate of temperature rise up to 200 ° C. It has been found that the thermal conductivity of the insulating coating can be improved by controlling the amount of chromium hydroxide (Cr (OH) 3 ) generated.
  • Chromium hydroxide (Cr (OH) 3) is estimated to form some polymerization conditions in the coating, the thermal conductivity is improved when the ratio of chromium hydroxide (Cr (OH) 3) is increased. This effect is noticeable when chromium hydroxide (Cr (OH) 3 ) is present in the insulating coating in an amount of 30% or more in terms of chromium trioxide (Cr 2 O 3 ). Further, the effect is more remarkable when it is 45% or more, and the effect is more remarkable when it is 60% or more.
  • An organic reducing agent can be used to reduce dichromic acid.
  • the organic reducing agent greatly affects the production of chromium hydroxide (Cr (OH) 3 ), and in the embodiment of the present invention, a polyol compound can be used as the organic reducing agent.
  • generation of chromium hydroxide (Cr (OH) 3 ) is very narrow.
  • ethylene glycol, glycerin, and sucrose can be used as the polyol compound, and the addition ratio thereof is 1.2 times to 3.3 the equivalent of dichromate regarded as a trivalent oxidizing agent. 6 times.
  • the coating line, the drying line, and the cooling line for the insulating coating are continuously provided at the lower part of the horizontal annealing line, which is the preceding process. For this reason, the total equipment length for the processes from coating to drying is determined based on the furnace length of the annealing furnace. In addition, since the cooling is performed by air cooling, the cooling furnace is relatively long. As a result, the heating furnace is shortened, and the heating rate is determined due to restrictions on the heating furnace equipment. .
  • the present inventors further examined the heating rate determined from the restrictions on the equipment as described above from the viewpoint of the production of chromium hydroxide (Cr (OH) 3 ).
  • the present inventors have reduced the temperature rising rate in the temperature range of 50 ° C. to 200 ° C. to 10 ° C./second to 35 ° C./second, which is slower than the conventional temperature rising rate. It has been found that the ratio of (Cr (OH) 3 ) can be 30% or more. A sufficient amount of chromium hydroxide (Cr (OH) 3 ) is unlikely to be generated even when the temperature rising rate in the temperature range of 50 ° C. to 200 ° C.
  • the rate of temperature rise in the temperature range of 50 ° C. to 200 ° C. is preferably 10 ° C./second to 35 ° C./second, and more preferably 10 ° C./second to 20 ° C./second.
  • the rate of temperature rise in the temperature range of 200 ° C. or higher is not particularly limited, and may exceed 35 ° C./second. Above 200 ° C., the remaining reducing agent and the organic compound having a relatively small molecular weight such as a surfactant in the organic resin are volatilized, and the produced chromium hydroxide (Cr (OH) 3 ) is gradually reduced by heating reduction.
  • the reaction that is oxidized to chromate and the reaction that produces chromium trioxide (Cr 2 O 3 ) from chromium hydroxide (Cr (OH) 3 ) proceed simultaneously and are offset. For this reason, even if the temperature increase rate in the temperature range of 200 ° C. or higher exceeds 35 ° C./second, no particular problem occurs.
  • the heating temperature is preferably up to 400 ° C., and when heated above 400 ° C., decomposition of the organic resin tends to start.
  • the heating temperature is more preferably up to 350 ° C.
  • the organic resin contained in the insulating coating is one or a mixture or copolymer of styrene resin, acrylic resin, epoxy resin and polyimide resin, and the crystallization rate is 10% to 50%.
  • the organic resin a copolymer of a styrene resin and an acrylic resin is particularly preferable, and the crystallization rate can be easily controlled and the crystallization rate in various ranges.
  • the reason why the crystallization rate is 10% to 50% is that when it is less than 10%, the thermal conductivity tends to be low, and when it exceeds 50%, it tends to powder.
  • the content of the organic resin is preferably 0.01 to 0.5 parts by weight with respect to 1 part by weight of dichromate. This is because if the amount is less than 0.01 part by weight, the effect of adding the organic resin is small and it is difficult to obtain sufficient coating properties, and if it exceeds 0.5 part by weight, it is difficult to obtain sufficient heat resistance.
  • a more preferred range is 0.1 to 0.4 parts by weight, which is a particularly excellent range for dispersing organic resins. As a synergistic effect with a crystallization rate of 10% to 50%, an effect is also seen in improving the space factor.
  • the crystallization rate can be controlled by copolymerization conditions and subsequent treatment such as heating, the crystallization rate can be easily controlled by adding various nucleating agents.
  • Any nucleating agent can be used, but oxide-based nucleating agents such as silica, magnesium oxide, and talc are effective.
  • talc is effective for acrylic resins and epoxy resins. It is.
  • the coating amount of the organic resin is not particularly limited, but is preferably 0.5 g / m 2 to 4.0 g / m 2 . This is because if the coating amount is less than 0.5 g / m 2 , the crystallization is likely to proceed, and the control of the crystallization rate is difficult, and if it exceeds 4.0 g / m 2 , the tendency for the adhesion to decrease becomes remarkable.
  • the method for measuring the proportion of chromium hydroxide (Cr (OH) 3 ) is not particularly limited.
  • the strength ratio of Cr—O bond and Cr—OH bond by ESCA (electron spectroscopy for chemical analysis) method may be calculated from several depth profiles.
  • the method of subtracting the amount calculated from the O—Cr—OH bond peak from Cr (III) is preferable because it is simple.
  • the application method is not particularly limited, and may be applied using a roll coater, applied using a spray, or immersed. You may apply
  • the heating method is not particularly limited, and heating by a normal radiant furnace may be performed, or heating using electricity such as induction heating may be performed.
  • induction heating is preferable from the viewpoint of accuracy of heating rate control.
  • the improvement of the external appearance is remarkable as well as the improvement of the thermal conductivity.
  • the appearance is good, the commercial value is improved, but an improvement in accuracy when mechanically inspecting wrinkles of electromagnetic steel sheets such as holes and protrusions can be expected.
  • the film is fine and crystalline, it tends to become cloudy without being glossy, but it is smooth and highly uniform.
  • the coating is amorphous, it tends to be glossy, but the uniformity depending on the location tends to decrease.
  • the crystallization rate is appropriately controlled, it is possible to balance gloss, smoothness and uniformity, and a good appearance can be obtained.
  • the coating liquid shown in Table 1 is shown in Table 2 on the surface of a non-oriented electrical steel sheet having a thickness of 0.35 mm containing Si: 2.5%, Al: 0.5%, and Mn: 0.05%. It was applied under conditions.
  • the dichromate, prepared chromium flakes and Mg (OH) 2, Al ( OH) 3, CaO, metal hydroxides such as SrCO 3, an oxide or carbonate mixture heated metal dichromate A 50% aqueous solution was used.
  • organic resin styrene resin, acrylic resin, and epoxy resin were each used as a 30% emulsion solution, and the polyimide resin was used as a 30% dispersion solution. Further, a predetermined amount of a reducing agent was added to prepare a coating solution having the composition shown in Table 1.
  • Table 1 the value on the right side of the column “Organic resin: parts by weight” indicates the weight of the organic resin relative to 1 part by weight of dichromic acid, and the value in parentheses on the left side indicates the crystallization rate of the organic resin. Indicates. A crystallization rate of 0% means an amorphous state.
  • organic resin of Example 5 a nucleating agent added with 0.03 parts by weight of talc (ultra fine powder type) with respect to 1 part by weight of resin solids was used.
  • a roll coater was used, and the amount of roll reduction was adjusted so that the amount applied was 2 g / m 2 .
  • Chromium hydroxide content in the table was determined Cr (OH) 3 content from the peak of oxygen and chromium by ESCA (photoelectron spectroscopy).
  • composition described in the column of “dichromate” in Table 1 is the composition when adjusted to a 50 wt% solution.
  • the amount of reducing agent is the amount of reducing agent added to 1 part by weight of dichromate.
  • “EG” in the “reducing agent” column represents ethylene glycol
  • “GL” represents glycerin
  • “SU” represents sucrose.
  • the redox equivalent is 4 for ethylene glycol, 9 for glycerin, and 12 for sucrose when dichromic acid is 3. That is, with respect to 1 mol of dichromate, 1.33 mol of ethylene glycol was equivalent, 3 mol of glycerin was equivalent, and 4 mol of sucrose was equivalent.
  • the magnetic steel sheet on which the insulating coating is formed is processed into 30 mm square, and 80 sheets are laminated.
  • a pressure is applied at a pressure of 20 kgf / cm 2 on a heating element heated to 180 ° C. after being surrounded by a heat insulating material.
  • the temperature change disappears after 60 minutes, the temperature of the steel plate sample opposite to the heating element (pressure side) is measured, and the lower the temperature, the better the thermal conductivity.
  • the space factor was measured according to the method (C2550) defined in JIS (Japanese Industrial Standard).
  • Adhesion was evaluated based on the traces of the peeled adhesive tape after a sample of a magnetic steel sheet having an adhesive tape affixed to 10 mm, 20 mm, and 30 mm diameter metal bars was wound. What was not peeled off when wound on a metal rod with a diameter of 10 mm was taken as 10 mm ⁇ OK, and what was not peeled off when wound around a metal rod with a diameter of 20 mm was wound around a metal rod with a diameter of 30 mm In this case, the one that did not peel off was defined as 30 mm ⁇ OK. It can be said that the smaller the diameter of the metal rod that does not peel off, the higher the adhesion.
  • Corrosion resistance was evaluated by a salt spray test according to a method defined in JIS (Z2371). And the state of the rust after 7-hour progress was evaluated in 10 steps. “10” indicates that rust was not generated, and “9” indicates that the ratio (area ratio) of the area where rust was generated was extremely small, greater than 0% and 0.1% or less. “7” indicates that the area ratio of rust is greater than 0.25% and 0.50% or less, and “6” indicates that the area ratio of rust is greater than 0.50% and less than 1.00%. Indicates that there was. Although not in Table 2, “1” indicates that the area ratio of rust was greater than 25% and 50% or less.
  • the glossy, smooth and uniform is 5 and the gloss is 4 but the uniformity is slightly inferior to that of the evaluation 5.
  • the slightly glossy and smooth but uniform. Those inferior to those of evaluation 5 were set to 3. Although not in Table 2, the gloss was less than that of evaluation 5, the smoothness was slightly inferior and the uniformity was inferior, and the gloss, uniformity and smoothness were inferior.
  • test Nos. within the scope of the present invention.
  • test Nos. 1 to 6 Examples
  • test No. Compared with 7 to 12 comparative examples
  • the temperature measured by thermal conductivity evaluation was lower, the space factor was higher, the adhesion was higher, the corrosion resistance was higher, and the appearance was better. From this result, the effect by this invention is clear.
  • the form of chromate can be controlled and the production rate of chromium hydroxide can be controlled.
  • the thermal conductivity of the insulating coating of the non-oriented electrical steel sheet can be improved, and a non-oriented electrical steel sheet with good heat dissipation can be obtained.

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  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
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Abstract

An electromagnetic steel sheet comprises an electromagnetic steel sheet and an insulating coating film formed on the surface of the electromagnetic steel sheet. The insulating coating film is mainly composed of: a chromic acid metal salt; and a mixture or a copolymer of one or more members selected from a styrene resin, an acrylic resin, an epoxy resin and a polyimide resin, which has a rate of crystallization of 10 to 50% and is contained in an amount of 0.01 to 0.5 part by weight relative to 1 part by weight of the chromic acid metal salt (in terms of the CrO3 content). In the insulating coating film, a chromium hydroxide compound is contained as a chromic acid compound in an amount of 30% or more in terms of the chromium (III) oxide (Cr2O3) content relative to the total amount (100%) of the chromic acid compound in terms of the chromium (III) oxide (Cr2O3) content.

Description

熱伝導性に優れた絶縁被膜を持つ電磁鋼板及びその製造方法Electrical steel sheet having an insulating coating excellent in thermal conductivity and method for producing the same
　本発明は、電気機器の鉄芯等に好適な熱伝導性に優れた絶縁被膜を持つ電磁鋼板及びその製造方法に関する。 The present invention relates to an electromagnetic steel sheet having an insulating coating excellent in thermal conductivity suitable for an iron core or the like of electrical equipment and a method for manufacturing the same.
　電気機器の高効率化及び小型化は、地球環境の保全の観点、及び世界的な電力及びエネルギー節約の観点から近年強く要望されている。電気機器の高効率化及び小型化のために種々の技術が開発されている。モータ及び小型変圧器（トランス）等の鉄芯に使用されている電磁鋼板においては、磁気特性の向上及び加工性の向上等が求められている。 High efficiency and miniaturization of electrical equipment have been strongly demanded in recent years from the viewpoint of global environmental conservation and global power and energy saving. Various techniques have been developed to increase the efficiency and miniaturization of electrical equipment. Magnetic steel sheets used for iron cores such as motors and small transformers (transformers) are required to improve magnetic characteristics and workability.
　かかる電気機器の高効率化及び小型化のためには、モータの発熱（ジュール熱）を抑制することが有効である。従来、そのために、鉄芯及び巻き線の効率を高めたり、放熱板等を用いて抜熱性を高めたりしている。特にモータの高効率化及び小型化に伴う放熱性の向上のために、積層鉄芯からの抜熱が重要性を帯びてきている。 In order to increase the efficiency and miniaturization of such electrical equipment, it is effective to suppress the heat generation (joule heat) of the motor. Conventionally, for this purpose, the efficiency of iron cores and windings has been increased, or heat dissipation has been improved by using a heat sink or the like. In particular, heat removal from a laminated iron core has become important in order to improve heat dissipation associated with higher efficiency and downsizing of a motor.
　抜熱に関し、従来の電気機器では、モータで発生した熱は積層鉄芯の端部からケースに伝導され、ケースの表面から、放熱板がある場合には放熱板から、対流及び放射によって周囲に放散される。 With regard to heat extraction, in conventional electrical equipment, the heat generated by the motor is conducted from the end of the laminated iron core to the case, and from the surface of the case, if there is a heat sink, from the heat sink to the surroundings by convection and radiation. Dissipated.
　積層鉄芯の形成にあたっては、電磁鋼板を鉄芯の形状に打ち抜いてから積層している。但し、このような電気機器の鉄芯に使用される電磁鋼板の表面には絶縁被膜が設けられている。この絶縁被膜には、絶縁性の他に、耐蝕性、溶接性、密着性、及び耐熱性等の特性が必要とされている。 In forming the laminated iron core, the magnetic steel sheets are punched into the shape of the iron core and then laminated. However, an insulating coating is provided on the surface of the electromagnetic steel sheet used for the iron core of such an electric device. In addition to insulating properties, the insulating coating is required to have characteristics such as corrosion resistance, weldability, adhesion, and heat resistance.
　電磁鋼板の絶縁被膜に関する技術としては、特許文献１に開示されているように、重クロム酸塩と酢酸ビニル、ブタジエン－スチレン共重合物、アクリル樹脂等の有機樹脂エマルジョンを主成分とする処理液を用いて絶縁被膜を形成する方法がある。また、特許文献２に開示されているように、クロム酸水溶液とエマルジョンタイプの樹脂と有機還元剤を混合し、易溶性アルミニウム化合物、２価金属の酸化物等及びＨ３ＢＯ３、さらにクロム酸溶液中のＭｅ２＋／Ａｌ３＋のモル比が０～７．０、かつ（Ａｌ３＋＋Ｍｅ２＋）／ＣｒＯ３のモル比が０．２～０．５、Ｈ３ＢＯ３／ＣｒＯ３のモル比が０．１～１．５の範囲にある処理液を用いて絶縁被膜を形成する方法がある。 As a technique related to the insulating coating of an electrical steel sheet, as disclosed in Patent Document 1, a treatment liquid mainly composed of an organic resin emulsion such as dichromate and vinyl acetate, a butadiene-styrene copolymer, an acrylic resin, etc. There is a method of forming an insulating film by using. Moreover, as disclosed in Patent Document 2, a chromic acid aqueous solution, an emulsion type resin, and an organic reducing agent are mixed, and a readily soluble aluminum compound, a divalent metal oxide, etc., H 3 BO 3 , and chromic acid are mixed. The molar ratio of Me 2+ / Al 3+ in the solution is 0 to 7.0, the molar ratio of (Al 3+ + Me 2+ ) / CrO 3 is 0.2 to 0.5, and the molar ratio of H 3 BO 3 / CrO 3 There is a method of forming an insulating film using a treatment liquid having a thickness of 0.1 to 1.5.
　特許文献３には、クロム酸、易溶性の２価及び／又は３価塩基性金属化合物、水性エマルジョン樹脂、ホウ酸、及び有機還元剤を含有する処理液の塗布と焼付け、歪取焼鈍後に、Ｘ線光電子分光法で測定して、被膜の外面側最表層に存在する、クロムが６価クロムからなる電磁鋼板が記載されている。 In Patent Document 3, after application and baking of a treatment liquid containing chromic acid, a readily soluble divalent and / or trivalent basic metal compound, an aqueous emulsion resin, boric acid, and an organic reducing agent, and after strain relief annealing, A magnetic steel sheet is described in which chromium is hexavalent chromium and is present on the outermost surface layer of the coating as measured by X-ray photoelectron spectroscopy.
　ところが、酸化物系の絶縁被膜の熱伝導率は金属よりも極めて低い。このため、鉄芯の積層方向には熱が伝わりにくく、この方向の放熱はモータ全体の放熱にあまり寄与していない。 However, the thermal conductivity of oxide-based insulating coatings is much lower than that of metals. For this reason, heat is not easily transmitted in the stacking direction of the iron cores, and heat dissipation in this direction does not contribute much to the heat dissipation of the entire motor.
　最近では様々な形状のモータが開発されている。そして、特に扁平なモータ等の積層鉄芯の端面からの抜熱が十分とはいえないモータにおいて、積層鉄芯のモータ軸方向の熱伝導性の向上が求められることが増加している。 Recently, various types of motors have been developed. In particular, in motors that do not have sufficient heat removal from the end face of the laminated iron core, such as a flat motor, there is an increasing demand for improved thermal conductivity in the motor axial direction of the laminated iron core.
　このように、特に、モータの直径に対して積層鉄芯の厚さが比較的短く、積層鉄芯の端面からの放熱が効果的でない場合、及び放熱板の取付け位置から積層方向に熱伝導させた方が効果的である場合に、放熱性が十分ではない。これは、従来の電磁鋼板では絶縁被膜が十分な熱伝導性を持たないためである。 In this way, in particular, when the thickness of the laminated iron core is relatively short with respect to the motor diameter, and heat radiation from the end surface of the laminated iron core is not effective, and heat conduction from the mounting position of the heat sink to the lamination direction. If it is more effective, heat dissipation is not sufficient. This is because the insulating coating does not have sufficient thermal conductivity in the conventional electrical steel sheet.
　また、熱伝導性が比較的高い絶縁被膜もあるが、一般的な電磁鋼板の絶縁被膜に求められる密着性、耐蝕性、作業性、絶縁性等の特性が得られない。また、占積率が低下してしまう。 In addition, although there are insulating coatings with relatively high thermal conductivity, characteristics such as adhesion, corrosion resistance, workability, and insulation required for insulating coatings of general electrical steel sheets cannot be obtained. In addition, the space factor decreases.
特公昭５０－１５０１３号公報Japanese Patent Publication No. 50-15013 特開平３－３６２８４号公報JP-A-3-36284 特開平６－１０１４９号公報Japanese Patent Laid-Open No. 6-10149
　本発明の目的は、絶縁被膜の密着性等を高く維持しながら、熱伝導率を向上させることができる熱伝導性に優れた絶縁被膜を持つ電磁鋼板及びその製造方法を提供することにある。 An object of the present invention is to provide an electrical steel sheet having an insulating coating excellent in thermal conductivity that can improve thermal conductivity while maintaining high adhesion of the insulating coating and the like, and a method for manufacturing the same.
　本発明に係る熱伝導性に優れた絶縁被膜を持つ電磁鋼板は、電磁鋼板と、前記電磁鋼板の表面に形成された絶縁被膜と、を有し、前記絶縁被膜は、クロム酸金属塩と、前記クロム酸金属塩（ＣｒＯ３に換算して）の１重量部に対して０．０１～０．５重量部の、結晶化率が１０～５０％である、スチレン樹脂、アクリル樹脂、エポキシ樹脂、ポリイミド樹脂の１種又は２種以上の混合物若しくは共重合物と、を主成分とし、クロム酸化合物として水酸化クロム化合物を、３酸化クロム（Ｃｒ２Ｏ３）に換算したクロム酸化合物１００％に対して３酸化クロム（Ｃｒ２Ｏ３）換算で３０％以上含有することを特徴とする。 An electrical steel sheet having an insulating coating excellent in thermal conductivity according to the present invention includes an electrical steel sheet and an insulating coating formed on a surface of the electromagnetic steel sheet, and the insulating coating includes a metal chromate salt, Styrene resin, acrylic resin, epoxy resin having a crystallization ratio of 0.01 to 0.5 parts by weight with respect to 1 part by weight of the chromic acid metal salt (in terms of CrO 3 ) 100% of a chromic acid compound obtained by converting a chromium hydroxide compound as a chromic acid compound into chromium trioxide (Cr 2 O 3 ) as a main component, one or a mixture of two or more kinds of polyimide resins or a copolymer. In contrast, it is characterized by containing 30% or more in terms of chromium trioxide (Cr 2 O 3 ).
　本発明に係る熱伝導性に優れた絶縁被膜を持つ電磁鋼板の製造方法は、電磁鋼板の表面に、所定のコーティング液を塗布する工程と、前記所定のコーティング液を乾燥させて絶縁被膜を形成する工程と、を有し、前記所定のコーティング液として、クロム酸金属塩と、前記クロム酸金属塩（ＣｒＯ３に換算して）の１重量部に対して樹脂固形分に換算して０．０１～０．５重量部の、結晶化率が１０％～５０％である、スチレン樹脂エマルジョン、アクリル樹脂エマルジョン、エポキシ樹脂エマルジョン、ポリイミド樹脂ディスパージョンの１種又は２種以上の混合物若しくは共重合物と、を主成分とし、クロム酸還元剤としてのポリオール化合物がクロム酸当量の１．２～３．６倍添加されたものを用い、前記絶縁被膜を形成する工程は、前記所定のコーティング液を、５０℃～２００℃の温度範囲において１０℃／秒～３５℃／秒の速度で加熱する工程を有することを特徴とする。 According to the present invention, there is provided a method of manufacturing an electrical steel sheet having an insulating coating having excellent thermal conductivity, a step of applying a predetermined coating liquid to the surface of the electrical steel sheet, and forming the insulating coating by drying the predetermined coating liquid And converting the resin solid content to 0.1 parts by weight with respect to 1 part by weight of the chromic acid metal salt and the chromic acid metal salt (in terms of CrO 3 ) as the predetermined coating liquid. 01 to 0.5 parts by weight of a styrene resin emulsion, an acrylic resin emulsion, an epoxy resin emulsion, a polyimide resin dispersion, or a mixture or copolymer of styrene resin emulsion, acrylic resin emulsion, epoxy resin dispersion having a crystallization rate of 10% to 50% And a main component, and a step of forming the insulating coating using a polyol compound as a chromic acid reducing agent added in an amount of 1.2 to 3.6 times the chromic acid equivalent, And heating the predetermined coating liquid at a rate of 10 ° C./second to 35 ° C./second in a temperature range of 50 ° C. to 200 ° C.
　以下、本発明の実施形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
　本発明の実施形態に係る電磁鋼板には、Ｓｉ：０．１質量％以上、Ａｌ：０．０５質量％以上含有されていることが好ましい。Ｓｉの含有量が増加するに従って、電気抵抗が大きくなって磁気特性が向上するが、脆性が増大する。このため、Ｓｉの含有量は４．０質量％未満であることが好ましい。Ａｌの含有量が増加するに従って、磁気特性が向上するが、圧延性が低下する。このため、Ａｌの含有量は３．０質量％未満であることが好ましい。 The electrical steel sheet according to the embodiment of the present invention preferably contains Si: 0.1% by mass or more and Al: 0.05% by mass or more. As the Si content increases, the electrical resistance increases and the magnetic properties improve, but the brittleness increases. For this reason, it is preferable that content of Si is less than 4.0 mass%. As the Al content increases, the magnetic properties are improved, but the rollability is lowered. For this reason, it is preferable that content of Al is less than 3.0 mass%.
　Ｓｉ及びＡｌ以外に、Ｍｎ等が含有されていてもよい。Ｍｎの含有量は０．０１質量％～１．０質量％であることが好ましい。また、Ｃｒ及びＮｉ等の遷移元素の含有量は０．１質量％未満であることが好ましく、０．０１質量％未満であることがより好ましい。また、Ｓ、Ｎ及びＣ等の典型元素の含有量は１００ｐｐｍ未満であることが好ましく、２０ｐｐｍ未満であることがより好ましい。 Mn etc. may be contained in addition to Si and Al. The Mn content is preferably 0.01% by mass to 1.0% by mass. In addition, the content of transition elements such as Cr and Ni is preferably less than 0.1% by mass, and more preferably less than 0.01% by mass. Further, the content of typical elements such as S, N and C is preferably less than 100 ppm, and more preferably less than 20 ppm.
　本発明の実施形態に係る電磁鋼板の製造に当たっては、例えば、上記の成分を有するスラブを熱間圧延し、コイル状に巻き取り、必要に応じて焼鈍し、厚さが０．１５ｍｍ～０．５ｍｍ程度まで冷間圧延し、更に焼鈍する。 In the production of the electrical steel sheet according to the embodiment of the present invention, for example, the slab having the above components is hot-rolled, wound into a coil shape, annealed as necessary, and has a thickness of 0.15 mm to 0.005. Cold-roll to about 5 mm and further anneal.
　なお、本発明の実施形態に係る電磁鋼板の表面粗度は比較的小さいことが好ましい。これは、高い密着性を得るためである。そして、圧延方向及び圧延方向に直交する方向における中心線平均粗さＲａは０．８μｍ以下であることが好ましく、０．５μｍ～０．１μｍであることがより好ましい。平均粗さＲａが０．８μｍより大きい場合、十分な曲げ密着性が得られないことがあるからである。 Note that the surface roughness of the electrical steel sheet according to the embodiment of the present invention is preferably relatively small. This is to obtain high adhesion. The center line average roughness Ra in the rolling direction and the direction orthogonal to the rolling direction is preferably 0.8 μm or less, and more preferably 0.5 μm to 0.1 μm. This is because if the average roughness Ra is larger than 0.8 μm, sufficient bending adhesion may not be obtained.
　本発明の実施形態に係る電磁鋼板の表面には、クロム酸金属塩及び有機樹脂を含む絶縁被膜が形成されている。クロム酸金属塩は、重クロム酸及び金属イオンを主成分とする水溶液を乾燥させたときの固形分となる。２価の陰イオンとみなした重クロム酸に対し、金属種をモル比で０．５～１．３含有していることが好ましい。また、金属種が２価の場合には、金属種のモル比が１．０５～１．１５であることがより好ましく、金属種が３価の場合には、金属種のモル比が０．７～０．７７であることがより好ましい。 An insulating coating containing a metal chromate and an organic resin is formed on the surface of the electrical steel sheet according to the embodiment of the present invention. The chromic acid metal salt becomes a solid content when an aqueous solution mainly containing dichromic acid and metal ions is dried. The metal species is preferably contained in a molar ratio of 0.5 to 1.3 with respect to dichromic acid regarded as a divalent anion. Further, when the metal species is divalent, the molar ratio of the metal species is more preferably 1.05 to 1.15. When the metal species is trivalent, the molar ratio of the metal species is 0.00. It is more preferably 7 to 0.77.
　また、金属イオンとしては、Ｌｉ、Ａｌ、Ｍｇ、Ｃａ、Ｓｒ、及びＴｉ等の軽金属のイオンが好ましく、Ｍｇ等のアルカリ土類金属のイオンが特に好ましい。重クロム酸溶液に金属イオンを溶解させる際には、金属イオンの酸化物、炭酸塩、又は水酸化物を用いてもよい。特に、Ｌｉ等のアルカリ金属のイオン及びＭｇ等のアルカリ土類金属のイオンを溶解させる際には、金属そのものを溶解させようとすると激しく反応するため、酸化物又は水酸化物を用いることが好ましい。 The metal ions are preferably light metal ions such as Li, Al, Mg, Ca, Sr, and Ti, and particularly preferably alkaline earth metal ions such as Mg. When metal ions are dissolved in the dichromic acid solution, metal ion oxides, carbonates, or hydroxides may be used. In particular, when an alkali metal ion such as Li and an alkaline earth metal ion such as Mg are dissolved, an attempt to dissolve the metal itself reacts violently, so it is preferable to use an oxide or hydroxide. .
　従来の電磁鋼板の製造に際して、重クロム酸塩溶液を２００℃以上に加熱乾燥させて形成した絶縁被膜中では、塗布された重クロム酸のクロムが６価から３価に還元され、クロムの大部分が３酸化クロム（Ｃｒ２Ｏ３）になり、クロムの１０％～２０％が水酸化クロム（Ｃｒ（ＯＨ）３）になっている。 In the production of the conventional electrical steel sheet, in the insulating coating formed by heating and drying the dichromate solution to 200 ° C. or higher, the chromium of the applied dichromic acid is reduced from hexavalent to trivalent, The portion is chromium trioxide (Cr 2 O 3 ), and 10% to 20% of chromium is chromium hydroxide (Cr (OH) 3 ).
　これに対し、本発明者らは、重クロム酸塩溶液を２００℃以上に加熱乾燥した場合でも、条件によって水酸化クロム（Ｃｒ（ＯＨ）３）の割合が従来のものよりも大きく増えることがあることを見出した。即ち、本発明者らは、水酸化クロム（Ｃｒ（ＯＨ）３）の生成量はポリオール化合物の添加量及び２００℃までの昇温速度に依存していることを見出した。そして、水酸化クロム（Ｃｒ（ＯＨ）３）の生成量を制御することにより、絶縁被膜の熱伝導性を改善することが可能であることが判明した。 On the other hand, even when the present inventors heat-dry the dichromate solution to 200 ° C. or higher, the ratio of chromium hydroxide (Cr (OH) 3 ) may increase more than the conventional one depending on conditions. I found out. That is, the present inventors have found that the amount of chromium hydroxide (Cr (OH) 3 ) produced depends on the amount of polyol compound added and the rate of temperature rise up to 200 ° C. It has been found that the thermal conductivity of the insulating coating can be improved by controlling the amount of chromium hydroxide (Cr (OH) 3 ) generated.
　水酸化クロム（Ｃｒ（ＯＨ）３）は被膜中で何らかの重合状態を形成していると推定され、水酸化クロム（Ｃｒ（ＯＨ）３）の割合が高くなると熱伝導性が向上する。そして、この効果が顕著に表れるのは、絶縁被膜中に水酸化クロム（Ｃｒ（ＯＨ）３）が３酸化クロム（Ｃｒ２Ｏ３）に換算して３０％以上存在するときである。また、４５％以上存在するときにより顕著に効果が表れ、６０％以上存在するときにより一層顕著に効果が表れる。 Chromium hydroxide (Cr (OH) 3) is estimated to form some polymerization conditions in the coating, the thermal conductivity is improved when the ratio of chromium hydroxide (Cr (OH) 3) is increased. This effect is noticeable when chromium hydroxide (Cr (OH) 3 ) is present in the insulating coating in an amount of 30% or more in terms of chromium trioxide (Cr 2 O 3 ). Further, the effect is more remarkable when it is 45% or more, and the effect is more remarkable when it is 60% or more.
　重クロム酸を還元するためには、有機還元剤を使用することができる。有機還元剤は水酸化クロム（Ｃｒ（ＯＨ）３）の生成に大きく影響を及ぼし、本発明の実施形態ではポリオール化合物を有機還元剤として使用することができる。また、水酸化クロム（Ｃｒ（ＯＨ）３）の生成を制御できるポリオール化合物の添加量は極めて狭い。具体的には、ポリオール化合物として、エチレングリコール、グリセリン、及びスクロースを使用することができ、その添加割合は、３価の酸化剤とみなした重クロム酸塩の当量の１．２倍～３．６倍である。１．２倍未満では水酸化クロム（Ｃｒ（ＯＨ）３）の生成が不十分で、十分な熱伝導性が得られにくく、３．６倍超では焼付け範囲が狭くなり、十分な作業性が得られにくいからである。重クロム酸当量の１．５～２．４倍とすることが好ましい。 An organic reducing agent can be used to reduce dichromic acid. The organic reducing agent greatly affects the production of chromium hydroxide (Cr (OH) 3 ), and in the embodiment of the present invention, a polyol compound can be used as the organic reducing agent. Moreover, the addition amount of the polyol compound which can control the production | generation of chromium hydroxide (Cr (OH) 3 ) is very narrow. Specifically, ethylene glycol, glycerin, and sucrose can be used as the polyol compound, and the addition ratio thereof is 1.2 times to 3.3 the equivalent of dichromate regarded as a trivalent oxidizing agent. 6 times. If it is less than 1.2 times, the production of chromium hydroxide (Cr (OH) 3 ) is insufficient, and it is difficult to obtain sufficient thermal conductivity, and if it exceeds 3.6 times, the baking range becomes narrow and sufficient workability is obtained. This is because it is difficult to obtain. It is preferably 1.5 to 2.4 times the dichromic acid equivalent.
　従来、無方向性電磁鋼板に対する絶縁被膜の形成に関し、絶縁被膜の塗布ライン、乾燥ライン及び冷却ラインは、これらの前工程である横型焼鈍ラインの下部に一続きで設けられている。このため、塗布から乾燥までの工程のための合計の設備長は焼鈍炉の炉長に基づいて決められている。また、冷却は空冷で行われているため、冷却炉は比較的長くなっており、この結果、昇温炉は短くなっており、昇温炉の設備に関する制約から昇温速度が決められている。 Conventionally, regarding the formation of an insulating coating on a non-oriented electrical steel sheet, the coating line, the drying line, and the cooling line for the insulating coating are continuously provided at the lower part of the horizontal annealing line, which is the preceding process. For this reason, the total equipment length for the processes from coating to drying is determined based on the furnace length of the annealing furnace. In addition, since the cooling is performed by air cooling, the cooling furnace is relatively long. As a result, the heating furnace is shortened, and the heating rate is determined due to restrictions on the heating furnace equipment. .
　これに対し、本発明者らは、前述のように設備に関する制約から決められている昇温速度について、水酸化クロム（Ｃｒ（ＯＨ）３）の生成の観点から更に検討を行った。この結果、本発明者らは、５０℃～２００℃の温度範囲での昇温速度を１０℃／秒～３５℃／秒と、従来の昇温速度と比べて遅くすることにより、水酸化クロム（Ｃｒ（ＯＨ）３）の割合を３０％以上とすることができることを見出した。５０℃～２００℃の温度範囲での昇温速度が１０℃／秒未満でも、３５℃／秒超でも、十分な量の水酸化クロム（Ｃｒ（ＯＨ）３）が生成しにくい。従って、５０℃～２００℃の温度範囲での昇温速度は、１０℃／秒～３５℃／秒とすることが好ましく、１０℃／秒～２０℃／秒とすることがより好ましい。 On the other hand, the present inventors further examined the heating rate determined from the restrictions on the equipment as described above from the viewpoint of the production of chromium hydroxide (Cr (OH) 3 ). As a result, the present inventors have reduced the temperature rising rate in the temperature range of 50 ° C. to 200 ° C. to 10 ° C./second to 35 ° C./second, which is slower than the conventional temperature rising rate. It has been found that the ratio of (Cr (OH) 3 ) can be 30% or more. A sufficient amount of chromium hydroxide (Cr (OH) 3 ) is unlikely to be generated even when the temperature rising rate in the temperature range of 50 ° C. to 200 ° C. is less than 10 ° C./second or more than 35 ° C./second. Accordingly, the rate of temperature rise in the temperature range of 50 ° C. to 200 ° C. is preferably 10 ° C./second to 35 ° C./second, and more preferably 10 ° C./second to 20 ° C./second.
　昇温速度が上記の範囲から外れた場合に十分な量の水酸化クロム（Ｃｒ（ＯＨ）３）が生成しにくい理由の詳細は明らかではない。１０℃／秒未満では熱力学的に安定な３酸化クロム（Ｃｒ２Ｏ３）の生成量が相対的に増大するためであると推定される。また、３５℃／秒超では、ポリオールの蒸発が速く、クロム酸の還元反応に寄与するポリオールの割合が低下して、加熱還元による重クロム酸塩の還元反応が支配的になるためであると推定される。 Details of the reason why it is difficult to produce a sufficient amount of chromium hydroxide (Cr (OH) 3 ) when the rate of temperature rise is out of the above range are not clear. If it is less than 10 ° C./second, it is estimated that this is because the amount of thermodynamically stable chromium trioxide (Cr 2 O 3 ) is relatively increased. In addition, when it exceeds 35 ° C./second, the polyol evaporates quickly, the ratio of the polyol contributing to the reduction reaction of chromic acid decreases, and the reduction reaction of dichromate by heat reduction becomes dominant. Presumed.
　２００℃以上の温度域での昇温速度は特に限定するものではなく、３５℃／秒を超えていてもよい。２００℃以上では、残存する還元剤及び有機樹脂中の界面活性剤等の比較的分子量が小さい有機化合物が揮発すると共に、生成した水酸化クロム（Ｃｒ（ＯＨ）３）が加熱還元により少しずつ重クロム酸塩に酸化される反応と、水酸化クロム（Ｃｒ（ＯＨ）３）から３酸化クロム（Ｃｒ２Ｏ３）が生成する反応とが同時に進行し、相殺される。このため、２００℃以上の温度域での昇温速度が３５℃／秒を超えていても、特に問題は生じない。 The rate of temperature rise in the temperature range of 200 ° C. or higher is not particularly limited, and may exceed 35 ° C./second. Above 200 ° C., the remaining reducing agent and the organic compound having a relatively small molecular weight such as a surfactant in the organic resin are volatilized, and the produced chromium hydroxide (Cr (OH) 3 ) is gradually reduced by heating reduction. The reaction that is oxidized to chromate and the reaction that produces chromium trioxide (Cr 2 O 3 ) from chromium hydroxide (Cr (OH) 3 ) proceed simultaneously and are offset. For this reason, even if the temperature increase rate in the temperature range of 200 ° C. or higher exceeds 35 ° C./second, no particular problem occurs.
　なお、加熱温度は４００℃までとすることが好ましく、４００℃を超えて加熱すると有機樹脂の分解が始まりやすい。加熱温度は、３５０℃までとすることがより好ましい。 It should be noted that the heating temperature is preferably up to 400 ° C., and when heated above 400 ° C., decomposition of the organic resin tends to start. The heating temperature is more preferably up to 350 ° C.
　絶縁被膜に含まれる有機樹脂は、スチレン樹脂、アクリル樹脂、エポキシ樹脂、ポリイミド樹脂の１種又は２種以上の混合物若しくは共重合物で、その結晶化率は１０％～５０％である。有機樹脂としては、特にスチレン樹脂とアクリル樹脂との共重合物が好ましく、結晶化率の制御が簡便でかつ様々な範囲の結晶化率とすることが可能である。結晶化率を１０％～５０％とするのは、１０％未満の場合、熱伝導性が低くなる傾向があり、５０％超では発粉する傾向があるためである。 The organic resin contained in the insulating coating is one or a mixture or copolymer of styrene resin, acrylic resin, epoxy resin and polyimide resin, and the crystallization rate is 10% to 50%. As the organic resin, a copolymer of a styrene resin and an acrylic resin is particularly preferable, and the crystallization rate can be easily controlled and the crystallization rate in various ranges. The reason why the crystallization rate is 10% to 50% is that when it is less than 10%, the thermal conductivity tends to be low, and when it exceeds 50%, it tends to powder.
　また、有機樹脂の含有量は、重クロム酸塩１重量部に対し、０．０１重量部～０．５重量部であることが好ましい。０．０１重量部未満では有機樹脂の添加の効果が少なく、十分な塗布性を得にくく、０．５重量部超では十分な耐熱性を得にくいためである。さらに好適な範囲は０．１重量部～０．４重量部であり、有機樹脂の分散にも特に優れた範囲である。１０％～５０％の結晶化率との相乗効果として、占積率の向上にも効果が認められる。 The content of the organic resin is preferably 0.01 to 0.5 parts by weight with respect to 1 part by weight of dichromate. This is because if the amount is less than 0.01 part by weight, the effect of adding the organic resin is small and it is difficult to obtain sufficient coating properties, and if it exceeds 0.5 part by weight, it is difficult to obtain sufficient heat resistance. A more preferred range is 0.1 to 0.4 parts by weight, which is a particularly excellent range for dispersing organic resins. As a synergistic effect with a crystallization rate of 10% to 50%, an effect is also seen in improving the space factor.
　共重合条件及びその後の加熱等の処理によって結晶化率を制御することも可能であるが、各種核化剤の添加により簡便に結晶化率を制御することも可能である。核化剤としては、どのようなものでも使用可能であるが、シリカ、酸化マグネシウム、及びタルク等の酸化物系核化剤が効果的であり、特にアクリル樹脂、エポキシ樹脂についてはタルクが効果的である。 Although the crystallization rate can be controlled by copolymerization conditions and subsequent treatment such as heating, the crystallization rate can be easily controlled by adding various nucleating agents. Any nucleating agent can be used, but oxide-based nucleating agents such as silica, magnesium oxide, and talc are effective. In particular, talc is effective for acrylic resins and epoxy resins. It is.
　有機樹脂の塗布量は特に限定するものではないが、０．５ｇ／ｍ２～４．０ｇ／ｍ２であることが好ましい。これは、塗布量が０．５ｇ／ｍ２未満では結晶化が進み易く結晶化率の制御が難しく、４．０ｇ／ｍ２超では密着性が低下する傾向が顕著になるためである。 The coating amount of the organic resin is not particularly limited, but is preferably 0.5 g / m 2 to 4.0 g / m 2 . This is because if the coating amount is less than 0.5 g / m 2 , the crystallization is likely to proceed, and the control of the crystallization rate is difficult, and if it exceeds 4.0 g / m 2 , the tendency for the adhesion to decrease becomes remarkable.
　水酸化クロム（Ｃｒ（ＯＨ）３）の割合を測定する方法は特に限定するものではない。例えば、ＥＳＣＡ（electron spectroscopy for chemical analysis）法によるＣｒ－Ｏ結合とＣｒ－ＯＨ結合との強度比を幾つかのデプスプロファイルから算出してもよい。特に、Ｃｒ（ＩＩＩ）からＯ－Ｃｒ－ＯＨ結合ピークから算出される量を差し引く方法が簡便であるため、好ましい。 The method for measuring the proportion of chromium hydroxide (Cr (OH) 3 ) is not particularly limited. For example, the strength ratio of Cr—O bond and Cr—OH bond by ESCA (electron spectroscopy for chemical analysis) method may be calculated from several depth profiles. In particular, the method of subtracting the amount calculated from the O—Cr—OH bond peak from Cr (III) is preferable because it is simple.
　絶縁被膜の形成に際し、処理液を電磁鋼板表面に塗布する場合、塗布の方法は特に限定するものではなく、ロールコーターを用いて塗布してもよく、スプレーを用いて塗布してもよく、浸漬（ディップ）により塗布してもよい。 In forming the insulating coating, when the treatment liquid is applied to the surface of the electrical steel sheet, the application method is not particularly limited, and may be applied using a roll coater, applied using a spray, or immersed. You may apply | coat by (dip).
　また、加熱の方法も特に限定されず、通常の輻射炉による加熱を行ってもよく、誘導加熱等の電気を用いた加熱を行ってもよい。但し、加熱速度の制御の精度の面から誘導加熱が好ましい。 Also, the heating method is not particularly limited, and heating by a normal radiant furnace may be performed, or heating using electricity such as induction heating may be performed. However, induction heating is preferable from the viewpoint of accuracy of heating rate control.
　本発明の実施形態によれば、熱伝導率の向上と共に外観の向上も顕著である。外観が良好であると商品価値が向上することは勿論であるが、穴及び突起等の電磁鋼板の瑕疵を機械的に検査する際の精度向上が期待できる。一般に被膜が微細な結晶質の場合、光沢が無く白濁する傾向があるが、平滑で均一性は高い。また、被膜が非晶質の場合には光沢が出る傾向があるが、場所による均一性が低下する傾向がある。本発明では、結晶化率を適切に制御されているために、光沢、平滑性及び均一性のバランスをとることが可能で、良好な外観が得られる。 According to the embodiment of the present invention, the improvement of the external appearance is remarkable as well as the improvement of the thermal conductivity. Of course, if the appearance is good, the commercial value is improved, but an improvement in accuracy when mechanically inspecting wrinkles of electromagnetic steel sheets such as holes and protrusions can be expected. In general, when the film is fine and crystalline, it tends to become cloudy without being glossy, but it is smooth and highly uniform. Further, when the coating is amorphous, it tends to be glossy, but the uniformity depending on the location tends to decrease. In the present invention, since the crystallization rate is appropriately controlled, it is possible to balance gloss, smoothness and uniformity, and a good appearance can be obtained.
　このように、特定の有機樹脂と特定の還元剤を含む重クロム酸塩溶液を特定の昇温速度で加熱することにより、クロム酸塩の形態を制御し、水酸化クロムの生成割合を制御することができる。この結果、無方向性電磁鋼板の絶縁被膜の熱伝導性を向上させ、放熱性の良い無方向性電磁鋼板を得ることができる。 Thus, by heating a dichromate solution containing a specific organic resin and a specific reducing agent at a specific temperature increase rate, the form of chromate is controlled and the production rate of chromium hydroxide is controlled. be able to. As a result, the thermal conductivity of the insulating coating of the non-oriented electrical steel sheet can be improved, and a non-oriented electrical steel sheet with good heat dissipation can be obtained.
　（実験例）
　Ｓｉ：２．５％、Ａｌ：０．５％、Ｍｎ：０．０５％を含有する厚さが０．３５ｍｍの無方向性電磁鋼板の表面に、表１に示すコーティング液を表２に示す条件で塗布した。重クロム酸塩としては、クロムフレークとＭｇ（ＯＨ）２、Ａｌ（ＯＨ）３、ＣａＯ、ＳｒＣＯ３等の金属水酸化物、酸化物又は炭酸塩を混合加熱して金属重クロム酸塩を調製し、５０％水溶液を用いた。 (Experimental example)
The coating liquid shown in Table 1 is shown in Table 2 on the surface of a non-oriented electrical steel sheet having a thickness of 0.35 mm containing Si: 2.5%, Al: 0.5%, and Mn: 0.05%. It was applied under conditions. The dichromate, prepared chromium flakes and Mg (OH) 2, Al ( OH) 3, CaO, metal hydroxides such as SrCO 3, an oxide or carbonate mixture heated metal dichromate A 50% aqueous solution was used.
　有機樹脂に関し、スチレン樹脂、アクリル樹脂、エポキシ樹脂はそれぞれ３０％エマルジョン溶液にして用い、ポリイミド樹脂は３０％ディスパージョン溶液にして用いた。さらに還元剤を所定量加えて、表１の組成のコーティング溶液を調整した。なお、表１中の「有機樹脂：重量部」の欄の右側の数値は、重クロム酸１重量部に対する有機樹脂の重量を示し、左側の（　）内の数値は、有機樹脂の結晶化率を示す。結晶化率０％は非晶質状態であることを意味する。 Regarding the organic resin, styrene resin, acrylic resin, and epoxy resin were each used as a 30% emulsion solution, and the polyimide resin was used as a 30% dispersion solution. Further, a predetermined amount of a reducing agent was added to prepare a coating solution having the composition shown in Table 1. In Table 1, the value on the right side of the column “Organic resin: parts by weight” indicates the weight of the organic resin relative to 1 part by weight of dichromic acid, and the value in parentheses on the left side indicates the crystallization rate of the organic resin. Indicates. A crystallization rate of 0% means an amorphous state.
　表１において、試験Ｎｏ．１、Ｎｏ．３及びＮｏ．５（実施例）の有機樹脂としては、核化剤としてタルク（超微粉タイプ）を樹脂固形分１重量部に対し０．０３重量部添加したものを使用した。コーティング液の塗布ではロールコーターを用い、塗布量が２ｇ／ｍ２になるようロール圧下量を調整した。 In Table 1, test no. 1, no. 3 and no. As the organic resin of Example 5 (Example), a nucleating agent added with 0.03 parts by weight of talc (ultra fine powder type) with respect to 1 part by weight of resin solids was used. In applying the coating solution, a roll coater was used, and the amount of roll reduction was adjusted so that the amount applied was 2 g / m 2 .
　乾燥は熱風炉を用いて行い、所定の昇温速度が得られるように炉温設定を調整した。到達温度はサンプルによって異なるが、２２５℃～４００℃の範囲になるよう調整した。得られたサンプルの評価測定結果を表２に示す。表中の水酸化クロム量はＥＳＣＡ（光電子分光分析法）により酸素とクロムのピークからＣｒ（ＯＨ）３量を決定した。 Drying was performed using a hot air furnace, and the furnace temperature setting was adjusted so that a predetermined rate of temperature increase was obtained. The ultimate temperature differs depending on the sample, but was adjusted to be in the range of 225 ° C to 400 ° C. Table 2 shows the evaluation measurement results of the obtained samples. Chromium hydroxide content in the table was determined Cr (OH) 3 content from the peak of oxygen and chromium by ESCA (photoelectron spectroscopy).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　なお、表１中の「重クロム酸塩」の欄に記載の組成は、５０重量％溶液に調整した時の組成である。還元剤の量は、重クロム酸塩の１重量部に対する還元剤の添加量である。「還元剤」の欄中の「ＥＧ」はエチレングリコールを示し、「ＧＬ」はグリセリンを示し、「ＳＵ」はスクロースを示している。酸化還元等量は、実験結果から、重クロム酸を３としたときに、エチレングリコールを４、グリセリンを９、スクロースを１２としている。即ち、１ｍｏｌの重クロム酸塩に対し、エチレングリコールは１．３３ｍｏｌを等量とし、グリセリンは３ｍｏｌを等量とし、スクロースは４ｍｏｌを等量とした。 In addition, the composition described in the column of “dichromate” in Table 1 is the composition when adjusted to a 50 wt% solution. The amount of reducing agent is the amount of reducing agent added to 1 part by weight of dichromate. “EG” in the “reducing agent” column represents ethylene glycol, “GL” represents glycerin, and “SU” represents sucrose. From the experimental results, the redox equivalent is 4 for ethylene glycol, 9 for glycerin, and 12 for sucrose when dichromic acid is 3. That is, with respect to 1 mol of dichromate, 1.33 mol of ethylene glycol was equivalent, 3 mol of glycerin was equivalent, and 4 mol of sucrose was equivalent.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　電磁鋼板の表面の熱伝導率を正確に測定することは困難であるため、以下の方法で評価した。絶縁被膜を形成した電磁鋼板を３０ｍｍ角に加工し、８０枚積層する。周囲を断熱材で囲ってから１８０℃に加熱した発熱体の上に、加圧力２０ｋｇｆ／ｃｍ２で加圧する。６０分後に温度変化が無くなったところで、発熱体と逆側（加圧側）の鋼板サンプルの温度を測定し、温度が低いものほど熱伝導率が良いと判断する。 Since it is difficult to accurately measure the thermal conductivity of the surface of the electrical steel sheet, it was evaluated by the following method. The magnetic steel sheet on which the insulating coating is formed is processed into 30 mm square, and 80 sheets are laminated. A pressure is applied at a pressure of 20 kgf / cm 2 on a heating element heated to 180 ° C. after being surrounded by a heat insulating material. When the temperature change disappears after 60 minutes, the temperature of the steel plate sample opposite to the heating element (pressure side) is measured, and the lower the temperature, the better the thermal conductivity.
　占積率はＪＩＳ（日本工業規格）に定められた方法（Ｃ２５５０）に準じて測定した。 The space factor was measured according to the method (C2550) defined in JIS (Japanese Industrial Standard).
　密着性は、１０ｍｍ、２０ｍｍ、３０ｍｍの直径の金属棒に粘着テープを貼った電磁鋼板のサンプルを巻きつけた後、粘着テープを引き剥がし、剥れた痕跡から評価した。直径が１０ｍｍの金属棒に巻きつけた場合に剥れなかったものを１０ｍｍφＯＫとし、直径が２０ｍｍの金属棒に巻きつけた場合に剥れなかったものを２０ｍｍφＯＫ、直径が３０ｍｍの金属棒に巻きつけた場合に剥れなかったものを３０ｍｍφＯＫとした。剥がれが生じない金属棒の直径が小さいものほど密着性が高いといえる。 Adhesion was evaluated based on the traces of the peeled adhesive tape after a sample of a magnetic steel sheet having an adhesive tape affixed to 10 mm, 20 mm, and 30 mm diameter metal bars was wound. What was not peeled off when wound on a metal rod with a diameter of 10 mm was taken as 10 mmφOK, and what was not peeled off when wound around a metal rod with a diameter of 20 mm was wound around a metal rod with a diameter of 30 mm In this case, the one that did not peel off was defined as 30 mmφOK. It can be said that the smaller the diameter of the metal rod that does not peel off, the higher the adhesion.
　耐蝕性の評価はＪＩＳに定められた方法（Ｚ２３７１）に準じた塩水噴霧試験により行った。そして、７時間経過後の錆の状態を１０段階で評価した。「１０」は錆の発生がなかったことを示し、「９」は錆が発生した面積の割合（面積率）が０％より大きく０．１％以下と極めて小さかったことを示す。また、「７」は錆の面積率が０．２５％より大きく０．５０％以下であったことを示し、「６」は錆の面積率が０．５０％より大きく１．００％以下であったことを示す。表２中にはないが、「１」は錆の面積率が２５％より大きく５０％以下であったことを示す。 Corrosion resistance was evaluated by a salt spray test according to a method defined in JIS (Z2371). And the state of the rust after 7-hour progress was evaluated in 10 steps. “10” indicates that rust was not generated, and “9” indicates that the ratio (area ratio) of the area where rust was generated was extremely small, greater than 0% and 0.1% or less. “7” indicates that the area ratio of rust is greater than 0.25% and 0.50% or less, and “6” indicates that the area ratio of rust is greater than 0.50% and less than 1.00%. Indicates that there was. Although not in Table 2, “1” indicates that the area ratio of rust was greater than 25% and 50% or less.
　外観の評価では、光沢があり、平滑で均一であるものを５とし、光沢はあるが均一性が評価５のものよりも若干劣るものを４とし、やや光沢があり平滑ではあるが均一性が評価５のものよりも劣るものを３とした。表２中にはないが、評価５のものと比較して、光沢が少なく、平滑性がやや劣り均一性が劣るものを２とし、光沢、均一性及び平滑性が劣るものを１とした。 In the evaluation of the appearance, the glossy, smooth and uniform is 5 and the gloss is 4 but the uniformity is slightly inferior to that of the evaluation 5. The slightly glossy and smooth but uniform. Those inferior to those of evaluation 5 were set to 3. Although not in Table 2, the gloss was less than that of evaluation 5, the smoothness was slightly inferior and the uniformity was inferior, and the gloss, uniformity and smoothness were inferior.
　表２に示すように、本発明の範囲内にある試験Ｎｏ．１～６（実施例）では、本発明範囲から外れる試験Ｎｏ．７～１２（比較例）と比較して、熱伝導性の評価で測定した温度が低く、占積率が高く、密着性が高く、耐蝕性が高く、外観が良好であった。この結果から、本発明による効果が明らかである。 As shown in Table 2, test Nos. Within the scope of the present invention. In Test Nos. 1 to 6 (Examples), test No. Compared with 7 to 12 (comparative examples), the temperature measured by thermal conductivity evaluation was lower, the space factor was higher, the adhesion was higher, the corrosion resistance was higher, and the appearance was better. From this result, the effect by this invention is clear.
　特定の有機樹脂と特定の還元剤を含む重クロム酸塩溶液を特定の昇温速度で加熱することにより、クロム酸塩の形態を制御し、水酸化クロムの生成割合を制御することができる。この結果、無方向性電磁鋼板の絶縁被膜の熱伝導性を向上させ、放熱性の良い無方向性電磁鋼板を得ることができる。
  By heating a dichromate solution containing a specific organic resin and a specific reducing agent at a specific temperature increase rate, the form of chromate can be controlled and the production rate of chromium hydroxide can be controlled. As a result, the thermal conductivity of the insulating coating of the non-oriented electrical steel sheet can be improved, and a non-oriented electrical steel sheet with good heat dissipation can be obtained.

Claims (7)

  1. 　電磁鋼板と、
    　前記電磁鋼板の表面に形成された絶縁被膜と、
    　を有し、
    　前記絶縁被膜は、
    　クロム酸金属塩と、前記クロム酸金属塩（ＣｒＯ３に換算して）の１重量部に対して０．０１～０．５重量部の、結晶化率が１０～５０％である、スチレン樹脂、アクリル樹脂、エポキシ樹脂、ポリイミド樹脂の１種又は２種以上の混合物若しくは共重合物と、を主成分とし、
    　クロム酸化合物として水酸化クロム化合物を、３酸化クロム（Ｃｒ２Ｏ３）に換算したクロム酸化合物１００％に対して３酸化クロム（Ｃｒ２Ｏ３）換算で３０％以上含有することを特徴とする熱伝導性に優れた絶縁被膜を持つ電磁鋼板。     Electrical steel sheet,
    An insulating coating formed on the surface of the electromagnetic steel sheet;
    Have
    The insulating coating is
    Styrene resin having a crystallization rate of 0.01 to 0.5 parts by weight with respect to 1 part by weight of the chromic acid metal salt and the chromic acid metal salt (in terms of CrO 3 ). An acrylic resin, an epoxy resin, a polyimide resin, or a mixture or copolymer of two or more,
    And characterized in that the chromium hydroxide compound as a chromic acid compound, containing chromium trioxide (Cr 2 O 3) chromium trioxide relative terms the chromic acid compound 100% (Cr 2 O 3) 30% or more in terms of Electrical steel sheet with an insulating coating with excellent thermal conductivity.
  2. 　前記絶縁被膜は、前記水酸化クロム化合物を、３酸化クロム（Ｃｒ２Ｏ３）に換算したクロム酸化合物１００％に対して３酸化クロム（Ｃｒ２Ｏ３）換算で４５％以上含有することを特徴とする請求項１に記載の熱伝導性に優れた絶縁被膜を持つ電磁鋼板。 The insulating coating contains 45% or more of the chromium hydroxide compound in terms of chromium trioxide (Cr 2 O 3 ) with respect to 100% of the chromate compound in terms of chromium trioxide (Cr 2 O 3 ). The electrical steel sheet having an insulating coating excellent in thermal conductivity according to claim 1.
  3. 　前記絶縁被膜は、前記水酸化クロム化合物を、３酸化クロム（Ｃｒ２Ｏ３）に換算したクロム酸化合物１００％に対して３酸化クロム（Ｃｒ２Ｏ３）換算で６０％以上含有することを特徴とする請求項１に記載の熱伝導性に優れた絶縁被膜を持つ電磁鋼板。 The insulating coating contains 60% or more of the chromium hydroxide compound in terms of chromium trioxide (Cr 2 O 3 ) with respect to 100% of the chromate compound in terms of chromium trioxide (Cr 2 O 3 ). The electrical steel sheet having an insulating coating excellent in thermal conductivity according to claim 1.
  4. 　電磁鋼板の表面に、所定のコーティング液を塗布する工程と、
    　前記所定のコーティング液を乾燥させて絶縁被膜を形成する工程と、
    　を有し、
    　前記所定のコーティング液として、クロム酸金属塩と、前記クロム酸金属塩（ＣｒＯ３に換算して）の１重量部に対して樹脂固形分に換算して０．０１～０．５重量部の、結晶化率が１０％～５０％である、スチレン樹脂エマルジョン、アクリル樹脂エマルジョン、エポキシ樹脂エマルジョン、ポリイミド樹脂ディスパージョンの１種又は２種以上の混合物若しくは共重合物と、を主成分とし、クロム酸還元剤としてのポリオール化合物がクロム酸当量の１．２倍～３．６倍添加されたものを用い、
    　前記絶縁被膜を形成する工程は、前記所定のコーティング液を、５０℃～２００℃の温度範囲において１０℃／秒～３５℃／秒の速度で加熱する工程を有することを特徴とする熱伝導性に優れた絶縁被膜を持つ電磁鋼板の製造方法。     Applying a predetermined coating liquid to the surface of the electrical steel sheet;
    Drying the predetermined coating liquid to form an insulating film;
    Have
    As the predetermined coating solution, 0.01 to 0.5 parts by weight in terms of resin solid content with respect to 1 part by weight of the chromic acid metal salt and the chromic acid metal salt (in terms of CrO 3 ). The main component is a styrene resin emulsion, an acrylic resin emulsion, an epoxy resin emulsion, or a mixture or copolymer of two or more of a styrene resin emulsion, an acrylic resin emulsion, an epoxy resin dispersion having a crystallization rate of 10% to 50%, and chromium. Using a polyol compound as an acid reducing agent added with 1.2 to 3.6 times the chromic acid equivalent,
    The step of forming the insulating film includes the step of heating the predetermined coating solution at a rate of 10 ° C./second to 35 ° C./second in a temperature range of 50 ° C. to 200 ° C. Of electrical steel sheet with excellent insulation coating.
  5. 　前記ポリオール化合物として、エチレングリコール、グリセリン又はスクロースを用いることを特徴とする請求項４に記載の熱伝導性に優れた絶縁被膜を持つ電磁鋼板の製造方法。 5. The method for producing an electrical steel sheet having an insulating coating excellent in thermal conductivity according to claim 4, wherein ethylene glycol, glycerin or sucrose is used as the polyol compound.
  6. 　前記所定のコーティング液として、前記クロム酸還元剤としてのポリオール化合物がクロム酸当量の１．５倍～２．４倍添加されたものを用いることを特徴とする請求項４に記載の熱伝導性に優れた絶縁被膜を持つ電磁鋼板の製造方法。 5. The thermal conductivity according to claim 4, wherein the predetermined coating liquid is a polyol compound as the chromic acid reducing agent added with 1.5 to 2.4 times the chromic acid equivalent. Of electrical steel sheet with excellent insulation coating.
  7. 　前記所定のコーティング液として、前記クロム酸還元剤としてのポリオール化合物がクロム酸当量の１．５倍～２．４倍添加されたものを用いることを特徴とする請求項５に記載の熱伝導性に優れた絶縁被膜を持つ電磁鋼板の製造方法。
          6. The thermal conductivity according to claim 5, wherein the predetermined coating liquid uses a polyol compound as the chromic acid reducing agent to which 1.5 to 2.4 times the chromic acid equivalent is added. Of electrical steel sheet with excellent insulation coating.
PCT/JP2009/053383 2008-03-13 2009-02-25 Electromagnetic steel sheet having insulating coating film with excellent thermal conductivity therein, and process for production thereof WO2009113392A1 (en)

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CN110832113A (en) * 2017-07-13 2020-02-21 日本制铁株式会社 Grain-oriented electromagnetic steel sheet
EP3808871A4 (en) * 2018-09-03 2021-08-25 JFE Steel Corporation Electromagnetic steel sheet having insulation coating film attached thereto, and method for producing same

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